Sunscreen composite particles dispersed in water-in-oil cosmetic compositions

ABSTRACT

A cosmetic water-in-oil emulsion composition is provided which includes composite particles of a sunscreen agent and a condensation polymerized polyamide binder, an emulsifying silicone surfactant sufficient to form the water-in-oil emulsion, an oil phase, and a water phase. The composition exhibits relatively high SPF photoprotection while maintaining excellent soft focus properties that hide skin imperfections.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention concerns cosmetic sunscreen compositions delivering UVprotection and also soft focus properties.

2. The Related Art

Ultraviolet radiation can be damaging to skin. Immediate damage may bein the form of erythema. More long term is the concern of initiatingcancerous growth. For these reasons, photoprotective agents known assunscreens have been incorporated into cosmetic products.

Facial cosmetics desirably deliver not only photoprotection but alsofunction to enhance overall skin appearance. Most persons have facialimperfections. These may include uneven tone, enlarged pores, fine linesand wrinkles.

Soft focus is an effect which can hide imperfect skin. Incoming light isdistorted by scattering (lensing). Particulate components of thecosmetic operate as lenses to bend and twist light into a variety ofdirections.

U.S. Pat. No. 5,997,890 (Sine et al.), U.S. Pat. No. 5,972,359 (Sine etal.), and U.S. Pat. No. 6,174,533 B1 (SaNogueira, Jr.) are all directedto topical compositions to provide good coverage of skin imperfections.The solution proposed by these documents is the use of a metal oxidewith a refractive index of at least about 2 and a neat primary particlesize of from about 100 to about 300 nm. Preferred particulates aretitanium dioxide, zirconium oxide and zinc oxide.

U.S. Patent Application 2005/0163813 A1 (Kosbach et al.) reports use offumed alumina particles for enhancing the soft-focus effect of certaincosmetic compositions.

Organic sunscreen agents can interfere with soft focus properties of acosmetic formulation. This is especially noticeable with formulas havingrelatively high levels of organic phase and/or emulsions with continuousoil phase characteristics. Consequently, there is a challenge to providecosmetics with a strong soft focus effect while maintaining a relativelyhigh degree of photoprotective benefits for the composition.

SUMMARY OF THE INVENTION

A water-in-oil emulsion cosmetic composition is provided which includes:

-   -   (i) from about 0.1 to about 20% by weight of composite particles        formed of an organic sunscreen agent and a condensation        polymerized polyamide in a relative weight ratio of about 5:1 to        about 1:10;    -   (ii) from about 0.1 to about 30% by weight of an emulsifying        silicone surfactant sufficient to form the water-in-oil        emulsion;    -   (iii) from about 1 to about 90% by weight of the composition of        the composition of an oil phase; and    -   (iv) from about 5 to about 90% by weight of the composition of        an aqueous phase.

DETAILED DESCRIPTION OF THE INVENTION

Now it has been found that a soft focus effect for hiding skin blemishescan co-exist with a sunscreen agent that can deliver a relatively highsunscreen protection factor (SPF). The invention requires an oilcontinuous phase emulsion known as a water-in-oil emulsion, especiallyachievable with an emulsifying silicone surfactant. Further, theinvention requires the presence of composite particles formed of organicsunscreen agent and a binder which is a condensation polymerizedpolyamide, especially a polyalkyleneoxypolyamide referred to as a “PAOPAResin” or an ester-terminated poly(ester-amide) referred to as “ETPEAResin”.

Relative weight ratio of organic sunscreen agent to polyamide may rangefrom about 5:1 to 1:10, preferably from about 3:1 to about 1:8, morepreferably from about 2:1 to about 1:7, optimally from about 1:1 toabout 1:3. Amounts of the polyamide may range from about 10% to about99.5% by weight of the composite particles. More preferably weight ofthe polyamide may range from about 30% to about 98%, optimally fromabout 50 to about 85% by weight of the composite particles. Amounts ofthe sunscreen agent may range from about 0.5 to about 90%, preferablyfrom about 2 to about 70%, optimally from about 30 to about 50% byweight of the composite particles.

Amounts of the composite particles within the cosmetic emulsioncomposition may range from about 0.1 to about 30%, preferably from about2 to about 15%, optimally from about 4 to about 10% by weight of thecosmetic composition.

Average particle size of the composite particles may range from about 10to about 2,000 nm, preferably from about 100 to about 1,500 nm, andoptimally from about 200 to about 1000 nm.

Sunscreen Composite Particles

Sunscreen particles of the present invention are formed as a compositeof an organic sunscreen agent and a binder which is a condensationpolymerization formed polyamide. Ester-terminated polyamides are mostuseful. Two examples are polyalkyleneoxypolyamide (PAOPA) andester-terminated poly(ester-amide) (ETPEA) resins.

The polyalkyleneoxypolyamide resins useful herein are outlined in U.S.Pat. No. 6,492,458 B1 herein incorporated by reference. These PAOPAmaterials may be prepared by combining reactants comprising amonocarboxylic acid compound, a diamine compound, and a dibasic acid.Specifics of these reactants are described hereinbelow. Commercially theresins are available from the Arizona Chemical Company under thetrademark Sylvaclear™ PA 1200V, designated by a INCI nomenclature asPolyamide-3. Exemplary monocarbyxlic acids of the formula R¹—COOHinclude, without limitation, stearic acid (C₁₈), 1-eicosanoic acid(C₂₀), 1-docasanoic acid (C₂₂, also known as behenic acid),dotricontanoic acid (C₃₂), tetratriacontanoic acid (C₃₄),pentatriacontanoic acid (C₃₅), tetracontanoic acid (C₄₀),tetraacontanioc acid (C₄₄), dopentaacontanoic acid (C₅₄),tetrahexaacontanoic acid (C₆₄), and dohexaacontanoic acid (C₇₂). Thesemonocarboxylic acids are available from many commercial suppliers,including Aldrich Chemical (Milwaukee, Wis.; www.sigma-aldrich.com).

Another suitable monocarboxylic acid is the oxidized (specifically,carboxyl terminated) polyethylene materials sold by Baker-Petrolite(Sugar Land, Tex.; www.bakerhughes.com/bapt/; division of Baker Hughes;www.bakerhughes.com) as their UNICID™ acids. UNICID™ acids are fullysaturated, linear carboxylic acids with average carbon chain lengthsranging from C24 to C50. Acid values for UNICID™ acids vary from 60 to115.

Still other suitable monocarboxylic acids are the alpha-branchedcarboxylic acids prepared by oxidizing higher molecular weight Guerbetalcohols. Such products are available from Jarchem Industries Inc.(Newark, N.J.; wwwjarchem.com) as their JARIC™ acids. JARIC™ 1-36 acidis a suitable monocarboxylic acid for the resins of this invention.

The diamine reactant has two amine groups, both of which are preferablyprimary amines, and is represented by the formulaHN(R^(2a))—R²—N(R^(2a))H. R^(2a) is preferably hydrogen, but may also bean alkyl group or may also join together with R² or another R^(2a) toform a heterocyclic structure. A preferred diamine is ethylene diamine,i.e., a diamine wherein R^(2a) is hydrogen and R² is —CH₂CH₂—.

Diamines other than ethylene diamine may be referred to herein asco-diamines. When present, co-diamines are preferably used in a minoramount compared to the ethylene diamine.

Exemplary co-diamines include 1,2-diaminopropane, 1,3-diaminopropane,1,4-diaminobutane, 1,2-diamino-2-methylpropane, 1,3-diaminopentane,1,5-diaminopentane, 2,3-dimethyl-1,3-propanediamine, 1,6-hexanediamine(also known as hexamethylenediamine, HMDA), 2-methyl-1,5-pentanediamine,1,7-diaminoheptane, 1,8-diaminooctane, 2,5-dimethyl-2,5-hexandeiamine,1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane,diaminophenanthrene (all isomers, including 9,10),4,4′-methylenebis(cyclohexylamine), 2,7-diaminofluorene, phenylenediamine (1,3; 1,3 and/or 1,4 isomers), adamantane diamine,2,4,6-trimethyl-1,3-phenylenediamine, 1,3-cyclohexanebis(methylamine),1,8-diamino-p-menthane, 2,3,5,6-tetramethyl-1,4-phenylenediamine,diaminoaphthalene (all isomers, including 1,5; 1,8; and 2,3) and4-amino-2,2,6,6-tetramethylpiperidine.

Suitable aromatic co-diamines (by which is meant molecules having tworeactive, preferably primary amine groups (—NH₂) and at least onearomatic ring (“Ar”) include xylene diamine and naphthalene diamine (allisomers).

Exemplary polyalkylene oxide-based co-diamines include withoutlimitation, the JEFAMINE™ diamines, i.e., poly(alkyleneoxy)diamines fromHuntsman Chemical (Salt Lake City, Utah), also known as polyetherdiamines. Preferred polyalkylene oxide-containing co-diamines are theJEFFAMINE® ED, XTJ and D series diamines.

In certain embodiments, the polyamide resins of the invention areprepared from co-diamine, where the co-diamine is selected from1,6-hexanediamine, xylenediamine, 1,2-propanediamine,2-methylpentamethylenediamine, and 1,12-dodecanediamine. Suitablediamines of the present invention are available from a number ofcommercial sources including Aldrich (Milwaukee, Wis.); EM Industries,Inc. (Hawthorne, N.Y.); Lancaster Synthesis, Inc. (Windham, N.H.) andSpectrum Quality Product, Inc. (New Brunswisk, N.J.).

The dibasic acid is an organic molecule containing two carboxylic acidgroups or reactive equivalent thereof. A preferred dibasic acid ispolymerized fatty acid, and in particular the dimer acid component ofpolymerized fatty acid. Polymerized fatty acid is typically a mixture ofstructures, including dimer acid and trimer acid, where individual dimeracids may be saturated, unsaturated, cyclic, acyclic, and combinationsthereof. Polymerized fatty acid is typically formed by heatinglong-chain unsaturated fatty acids, e.g., C₁₈ monocarboxylic acids, toabout 200-250° C. in the presence of a clay catalyst in order that thefatty acids polymerize. The product typically comprises dimer acid, i.e.C₃₆ dicarboxylic acid formed by dimerization of the fatty acid, andtrimer acid, i.e., C₅₄ tricarboxylic acid formed by trimerization of thefatty acid. A more detailed discussion of fatty acid polymerization maybe found in U.S. Pat. No. 3,157,681.

Because fatty acid polymerization typically forms much more dimer acidthan trimer acid, those skilled in the art may often refer topolymerized fatty acid as dimer acid, even though some trimer acid, andeven higher polymerization products, may be present with the dimer acid.It is preferred that the polymerized fatty acid contain less than about20 weight percent of trimer acid, based on the total weight of thepolymerized fatty acid, and that the dimer acid constitute at leastabout 80 weight percent of the polymerized fatty acid. More preferably,the dimer acid constitutes essentially all of the polymerized fattyacid.

Typical unsaturated fatty acids used to form polymerized fatty acidinclude oleic acid, linoleic acid and linolenic acid. Tall oil fattyacid, which is a mixture containing long-chain unsaturated fatty acidsobtained as a byproduct of the wood pulping process, is preferred forpreparing polymerized fatty acid.

Polymerized fatty acid may be hydrogenated prior to being used in theresin-forming reaction. Hydrogenation tends to provide for a slightlyhigher melting point and greater oxidative and color stability.

Polymerized fatty acid, dimer acid, and hydrogenated versions thereofmay be obtained from a number of commercial suppliers. For example,Arizona Chemical (Jacksonville, Fla.) sells polymerized fatty acid undertheir UNDYME® trademark.

In addition to polymerized fatty acid, or reactive equivalents thereof,the dibasic acid may comprise a co-diacid. An exemplary co-diacid is aso-called “linear” diacid of the formula HOOC—R¹—COOH wherein R¹ is alinear C₄₋₁₇ hydrocarbon group, and more preferably is a linear C₆₋₈hydrocarbon group. Linear co-diacids suitable for the present inventioninclude 1,6-hexanedioic acid (adipic acid), 1,7-heptanedioic acid(pimelic acid), 1-8-octanedioic acid (suberic acid), 1,9-nonanedioicacid (azelaic acid), 1,10-decanedioic acid (sebacic acid),1,11-undecanedioic acid, 1,12-dodecanedioic acid(1,10-decanedicarboxylic acid), 1,13-tridecanedioic acid (brassylicacid) and 1,14-tetradecanedioic acid (1,12-dodecanedicarboxylic acid).

Another exemplary co-diacid is the reaction product of acrylic ormethacrylic acid (or the ester thereof, with a subsequent hydrolysisstep to form an acid) and an unsaturated fatty acid. For example, a C₂₁diacid of this type may be formed by reacting acrylic acid with a C₁₈unsaturated fatty acid (e.g., oleic acid), where an ene-reactionpresumably occurs between the reactants. An exemplary C₂, diacid iscommercially available from Westvaco Corporation, Chemical Division,Charleston Heights, S.C. as their product number 1550.

Aromatic diacids may be used as the co-diacid. An “aromatic diacid” asused herein is a molecule having two carboxylic acid groups (—COOH) orreactive equivalents thereof (e.g., acid chloride (—COCl) or ester(—COOR) and at least one aromatic ring (“Ar”). Phthalic acids, e.g.,isophthalic acid and terephthalic acid, are exemplary aromatic diacids.

In one aspect, the resin is prepared with co-diacid and the co-diacid isselected from 1,4-cyclohexane dicarboxylic acid, isophthalic acid,adipic acid, azeleic acid, sebacic acid, and dodecandioic acid.

A second class of polyamides useful for this invention are theester-terminated poly(ester-amide) resins. These are prepared byreacting components comprising dibasic acid, diamine, polyol andmonoalcohol, wherein at least 50 equivalent percent of the dibasic acidcomprises polymerized fatty acid; and at least 50 equivalent percent ofthe diamine comprises ethylene diamine. Typical dibasic acids, anddiamines have already been described hereinabove.

A further constituent of the ester-terminated poly(ester-amide) resinsare the monoalcohol reactants. The monoalcohol may be represented by theformula R³—OH, wherein R³ is preferably a hydrocarbon group having atleast ten carbon atoms. Thus, the monoalcohol can also be described as amonohydric alcohol. In one aspect, R³ is a C₁₀₋₃₀ hydrocarbon,preferably a C₁₂₋₂₄ hydrocarbon, still more preferably is a C₁₆₋₂₂hydrocarbon, and yet still more preferably is a C₁₈ hydrocarbon.Preferably, R³ is linear, with the hydroxyl group located on a terminalcarbon atoms, i.e., the monoalcohol is a primary monoalcohol. Thus,1-dodecanol, 1-tetradecanol, 1-hexadecanol (cetyl alcohol),1-octadecanol (stearyl alcohol), 1-eicosanol (arachidyl alcohol) and1-docosanol (behenyl alcohol) are preferred monoalcohols for preparingpolyamide resin binders of the invention.

Another suitable monoalcohol reactant is a so-called Guerbet alcohol.Guerbet alcohols have the general formula H—C(Ra)(Rb)—CH₂—OH wherein Raand Rb may be the same or different and preferably represent a C₆₋₁₂hydrocarbon group.

Another suitable monoalcohol reactant is a linear wax alcohol. Suitablelinear wax alcohols are commercially available from, e.g., PetroliteCorporation (Tulsa, Okla.) under their UNILIN® trademark. These waxalcohols are typically a blend of linear alcohols having at least about20 carbon atoms, and more typically at least about 24 carbon atoms.

A final ingredient necessary in preparing an ETPEA resin of the presentinvention is polyol, which may also be referred to as polyhydricalcohol. The polyol is of the formula R⁴(OH)_(n) wherein R⁴ is ann-valent organic group. For instance, R⁴ may be a C₂-C₂₀ organic groupwithout hydroxyl substitution. As another example, R⁴ may be ahydrocarbon. Typically, n is selected from 2, 3, 4, 5 and 6. Suitablepolyols for use in preparing an ETPEA resin of the present inventioninclude ethylene glycol, propylene glycol, butylene glycol, glycerol,trimethylolpropane, pentaerythritol, neopentyl glycol,tris(hydroxylmethyl)methanol, di-pentaerythritol, andtri-pentaerthyritol.

Preparation and description of the ETPEA resins are found in U.S. Pat.No. 7,329,719 B2 herein incorporated by reference. Commercially theseresins are available from the Arizona Chemical Company under thetrademark Sylvaclear AF 1900V. These resins are easily intimately mixedwith OMC to form a composite particulate with photoprotective sunscreen.

Sunscreen agents can either be dispersed throughout the polyamide resinbinder or can be formed as a core surrounded by binder. Dispersalthroughout the binder is preferred.

Sunscreen agents according to this invention will have at least onechromophoric group absorbing within the ultraviolet ranging from 290 to400 nm. Chromophoric organic sunscreen agents may be divided into thefollowing categories (with specific examples) including: p-Aminobenzoicacid, its salts and its derivatives (ethyl, isobutyl, glyceryl esters;p-dimethylaminobenzoic acid); Anthranilates (o-aminobenzoates; methyl,menthyl, phenyl, benzyl, phenylethyl, linalyl, terpinyl, andcyclohexenyl esters); Salicylates (octyl, amyl, phenyl, benzyl, menthyl,glyceryl, and dipropyleneglycol esters); Cinnamic acid derivatives(menthyl and benzyl esters, alpha-phenyl cinnamonitrile; butyl cinnamoylpyruvate); Dihydroxycinnamic acid derivatives (umbelliferone,methylumbelliferone, methylaceto-umbelliferone); Trihydroxycinnamic acidderivatives (esculetin, methylesculetin, daphnetin, and the glucosides,esculin and daphnin); Hydrocarbons (diphenylbutadiene, stilbene);Dibenzalacetone and benzalacetophenone; Naphtholsulfonates (sodium saltsof 2-naphthol-3,6-disulfonic and of 2-naphthol-6,8-disulfonic acids);Dihydroxy-naphthoic acid and its salts; o- andp-Hydroxybiphenyldisulfonates; Coumarin derivatives (7-hydroxy,7-methyl, 3-phenyl); Diazoles (2-acetyl-3-bromoindazole, phenylbenzoxazole, methyl naphthoxazole, various aryl benzothiazoles); Quininesalts (bisulfate, sulfate, chloride, oleate, and tannate); Quinolinederivatives (8-hydroxyquinoline salts, 2-phenylquinoline); Hydroxy- ormethoxy-substituted benzophenones; Uric and vilouric acids; Tannic acidand its derivatives (e.g., hexaethylether); (Butyl carbityl) (6-propylpiperonyl)ether; Hydroquinone; Benzophenones (Oxybenzone, Sulisobenzone,Dioxybenzone, Benzoresorcinol, 2,2′,4,4′-Tetrahydroxybenzophenone,2,2′-Dihydroxy-4,4′-dimethoxybenzophenone, Octabenzone;4-Isopropyldibenzoylmethane; Butylmethoxydibenzoylmethane; Etocrylene;and 4-isopropyl-dibenzoylmethane).

Particularly useful sunscreen agents are: 2-ethylhexylp-methoxycinnamate, 4,4′-t-butyl methoxydibenzoylmethane,2-hydroxy-4-methoxybenzophenone (known also as Benzophenone-3),octyldimethyl p-aminobenzoic acid, digalloyltrioleate,2,2-dihydroxy-4-methoxybenzophenone, ethyl4-[bis(hydroxypropyl)]aminobenzoate,2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexylsalicylate,glyceryl p-aminobenzoate, 3,3,5-trimethylcyclohexylsalicylate,methylanthranilate, p-dimethylaminobenzoic acid or aminobenzoate,2-ethylhexyl p-dimethylaminobenzoate, 2-phenylbenzimidazole-5-sulfonicacid, 2-(p-dimethylaminophenyl)-5-sulfoniobenzoxazoic acid,4-methylbenzylidene camphor, bis-ethylhexyloxyphenol methoxyphenoltriazine, methylene bis-benzotriazolyl tetramethylbutylphenol,dimethicodiethylbenzal malonate, isoamyl methoxycinnamate, octyltriazone, terephthalidene dicamphor sulfonic acid and mixtures thereof.

Cosmetic compositions of this invention may not only have sunscreenagent held within the composite particles but also an amount ofsunscreen agent may be formulated free of binder within the composition.When present external of the composite, the sunscreen agent may beavailable in amounts from about 0.1 to about 25%, particularly fromabout 2 to about 15% by weight of the composition. Some preferredembodiments of this invention may be formulated without any sunscreenagent external to the composites or with only a relatively small amountof such material. For instance, external sunscreen agent may range inamount from about 0 to 5%, preferably from 0.01 to 2%, and possibly from0.01 to 0.8% by weight of the composition.

Water-in-Oil Silicone Surfactant

A wide variety of silicone surfactants are useful herein. Thesesilicones are typically non-crosslinked organically modifiedorganopolysiloxanes such as dimethicone copolyols.

Nonlimiting examples of dimethicone copolyols and other siliconesurfactants useful herein include polydimethylsiloxane polyethercopolymers with pendant polyethylene oxide side chains,polydimethylsiloxane polyether copolymers with pendant polypropyleneoxide side chains, polydimethylsiloxane polyether copolymers withpendant mixed polyethylenen oxide and polypropylene oxide side chains,polydimethylsiloxane polyether copolymers with pendant mixedpoly(ethylene)(propylene)oxide side chains, polydimethylsiloxanepolyether copolymers with pendant organobetaine side chains,polydimethylsiloxane polyether copolymers with pendant carboxylate sidechains, polydimethylsiloxane polyether copolymers with pendantquaternary ammonium side chains; and also further modifications of thepreceding copolymers containing pendant (C2-C30 straight, branched, orcyclic alkyl moieties. Examples of commercially available dimethiconecopolyols useful herein sold by Dow Corning Corporation are Dow Corning®190, 193, Q2-5220, 2501 Wax, 2-5324 fluid, and 5225C (this lattermaterial being sold as a mixture with cyclomethicone). Cetyl dimethiconecopolyol is commercially available as a mixture with polyglyceryl-4isostearate (and) hexyl laurate and is sold under the tradename ABIL®WS-08 (also available from Goldschmidt). Other nonlimiting examples ofdimethicone copolyols include lauryl dimethicone copolyol, dimethiconecopolyol acetate, dimethicone copolyol adipate, dimethiconecopolyolamine, dimethicone copolyol behenate, dimethicone copolyol butylether, dimethicone copolyol hydroxy stearate, dimethicone copolyolisostearate, dimethcione copolyol laurate, dimethicone copolyol methylether, dimethicone copolyol phosphate, dimethicone copolyolsulfosuccinate and dimethicone copolyol stearate. Most preferred isPEG-10 Dimethicone available from Shin Etsu.

Amounts of the silicone surfactant may range from about 0.1 to about30%, preferably from about 1 to about 10%, optimally from about 1.5 toabout 5% by weight of the composition.

Dispersed Aqueous Phase

The compositions of the present invention comprise from about 5% toabout 90%, more preferably from about 30% to about 75%, and even morepreferably from about 45% to about 60% of a dispersed aqueous phase. Inemulsion technology, the term “dispersed phase” means that the phaseexists as small particles or droplets suspended in and surrounded by acontinuous phase.

The aqueous phase can be water, or a combination of water and one ormore water soluble or dispersible ingredients. Nonlimiting examples ofsuch optional ingredients include but are not limited to thickeners,acids, bases, salts, chelants, gums, water-soluble or dispersiblealcohols and polyols, buffers, preservatives, and colorants.

Continuous Oil Phase

A continuous oil phase will be present in compositions of thisinvention. Amounts of the oil phase may range from about 1 to about 90%,preferably from about 20 to about 70%, optimally from about 30 to about60% by weight of the composition.

Typical components of the oil phase may be silicones, hydrocarbons,triglycerides and combinations thereof. More specific materials aredescribed hereinafter under the Optional Components section.

Optional Components

The composition of the present invention may contain a variety of othercomponents to enhance physical properties and performance. Thesecomponents may either constitute parts of the oil or the water phases.

A component optional to the present invention may be a crosslinkedsilicone (organopolysiloxane) elastomer. No specific restriction existsas to the type of curable organopolysiloxane composition that can serveas starting material for the crosslinked silicone elastomer. Examples inthis respect are addition reaction-curing organopolysiloxanecompositions which cure under platinum metal catalysis by the additionreaction between SiH-containing diorganopolysiloxane andorganopolysiloxane having silicon-bonded vinyl groups;condensation-curing organopolysiloxane compositions which cure in thepresence of an organotin compound by a dehydrogenation reaction betweenhydroxyl terminated diorganopolysiloxane and SiH-containingdiorganopolysiloxane; condensation-curing organopolysiloxanecompositions which cure in the presence of an organotin compound or atitanate ester, by a condensation reaction between a hydroxyl terminateddiorganopolysiloxane and a hydrolyzable organosilane (this condensationreaction is exemplified by dehydration, alcohol-liberating,oxime-liberating, amine-liberating, amide-liberating,carboxyl-liberating, and ketone-liberating reactions); peroxide-curingorganopolysiloxane compositions which thermally cure in the presence ofan organoperoxide catalyst; and organopolysiloxane compositions whichare cured by high-energy radiation, such as by gamma-rays, ultravioletradiation, or electron beams.

Ordinarily these materials are provided as a 1-30% crosslinked siliconeelastomer dissolved or suspended in a dimethicone fluid (usuallycyclomethicone). For purposes of definition “crosslinked siliconeelastomer” refers to the elastomer alone rather than the totalcommercial compositions which also include a solvent (e.g. dimethicone)carrier.

Dimethicone/vinyl dimethicone crosspolymers and dimethiconecrosspolymers are available from a variety of suppliers including DowCorning (9040, 9041, 9045, 9506 and 9509), General Electric (SFE 839),Shin Etsu (KSG-15, 16, 18 [dimethicone/phenyl vinyl dimethiconecrosspolymer]), and Grant Industries (Gransil™ line of materials), andlauryl dimethicone/vinyl dimethicone crosspolymers supplied by Shin Etsu(e.g., KSG-31, KSG-32, KSG-41, KSG-42, KSG-43, and KSG-44).

Other suitable commercially available silicone elastomer powders includevinyl dimethicone/methicone silesquioxane crosspolymers from Shin-Etsusold as KSP-100, KSP-101, KSP-102, KSP-103, KSP-104, KSP-105, and hybridsilicone powders that contain a fluoroalkyl group or a phenyl group soldby Shin-Etsu as respectively KSP-200 and KSP-300.

The crosslinked silicone elastomers may range in concentration fromabout 0.01 to about 30%, preferably from about 0.1 to about 10%,optimally from about 0.5 to about 2% by weight of the cosmeticcomposition. These weight values exclude any solvent such ascyclomethicone found in commercial “elastomer” silicones such as the DowCorning products 9040 and 9045. For instance, the amount of crosslinkedsilicone elastomer in 9040 and 9045 is between 12 and 13% by weight.

The optional components, when incorporated into the composition, shouldbe suitable for use in contact with human keratinous tissue withoutundue toxicity, incompatibility, instability, allergic response, and thelike within the scope of sound judgment. The CTFA Cosmetic IngredientHandbook, Second Edition (1992) describes a wide variety of nonlimitingcosmetic and pharmaceutical ingredients commonly used in the skin careindustry, which are suitable for use in the compositions of the presentinvention. Examples of these classes include: abrasives, absorbents,aesthetic components such as fragrances, pigments, colorings/colorants,essential oils, skin sensates, astringents, etc. (e.g. clove oil,menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch hazeldistillate), anti-acne agents, anti-caking agents, antifoaming agents,antimicrobial agents, antioxidants, biological additives, bufferingagents, bulking agents, chelating agents, chemical additives, colorants,cosmetic astringents, cosmetic biocides, denaturants, drug astringents,external analgesics, film forming polymers, opacifying agents, pHadjusters, propellants, reducing agents, sequestrants, skin bleachingand lightening agents, skin conditioning agents, skin soothing and/orhealing agents and derivatives, skin treating agents, thickeners, andvitamins and derivatives thereof.

In any embodiment of the present invention, however, the actives usefulherein can be categorized by the benefit they provide or by theirpostulated mode of action. However, it is to be understood that theactives useful herein can in some instances provide more than onebenefit or operate via more than one mode of action. Therefore,classifications herein are made for the sake of convenience and are notintended to limit the active to that particular application orapplications listed.

A safe and effective amount of an anti-oxidant/radical scavenger may beadded in amounts from about 0.01% to about 10%, more preferably fromabout 0.1% to about 5% by weight of the composition.

Anti-oxidants/radical scavengers may be employed such as ascorbic acid(vitamin C) and its salts, ascorbyl esters of fatty acids, ascorbic acidderivatives (e.g. magnesium ascorbyl phosphate), tocopherol (vitamin E),tocopherol sorbate, tocopherol acetate, other esters of tocopherol,butylated hydroxy benzoic acids and their salts,6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (commerciallyavailable under the tradename Trolor®), amines (e.g.N,N-diethylhydroxylamine, amino-guanidine), nordihydroguairetic acid,bioflavonoids, amino acids, silymarin, tea extracts, and grape skin/seedextracts. Preferred anti-oxidants/radical scavengers are selected fromesters of tocopherol, more preferably tocopherol acetate.

The compositions of the present invention may optionally comprise aflavonoid compound. Flavonoids are disclosed in U.S. Pat. Nos. 5,686,082and 5,686,367 herein incorporated by reference. Examples of flavonoidsparticularly suitable flavones, isoflavones, coumarins, chromones,discoumarols, chromanones, chromanols, isomers (e.g. cis/trans isomers)thereof, and mixtures thereof.

Preferred for use are flavones and isoflavones, in particular daidzein(7,4′-dihydroxy isoflavone), genistein (5,7,4′-trihydroxy isoflavone),equol (7,4′-dihydroxy isoflavan), 5,7-dihydroxy-4′-methoxy isoflavone,soy isoflavones (a mixture extracted from soy), and mixtures thereof.Flavonoid compounds useful herein are commercially available from anumber of sources, e.g., Indofine Chemical Company, Inc., Stearloids,Inc., and Aldrich Chemical Company, Inc. The herein described flavonoidcompounds are preferably present in from about 0.01% to about 20%, morepreferably from about 0.1% to about 10%, and even more preferably fromabout 0.5% to about 5% by weight.

Anti-inflammatory agents useful herein include allantoin and compoundsof the Licorice (the plant genus/species Glycyrrhiza glabra) family,including glycyrrhetic acid, glycyrrhizic acid, and derivatives thereof(e.g. salts and esters).

The compositions may comprise a tanning active. When present, it ispreferable that the compositions comprise from about 0.1% to about 20%,more preferably from about 2% to about 7% by weight of the composition.A preferred tanning active is dihydroxyacetone.

The compositions may comprise a skin lightening agent. When used, thecompositions preferably comprise from about 0.1% to about 10%, morepreferably from about 0.2% to about 5%, also preferably from about 0.5%to about 2%, by weight of the composition, of a skin lightening agent.Suitable skin lightening agents include niacinamide, kojic acid,arbutin, tranexamic acid, placental extract, ascorbic acid andderivatives thereof (e.g. magnesium ascorbyl phosphate, sodium ascorbylphosphate, ascorbyl glucoside, and ascorbyl tetraisopalmitates). Otherskin lightening materials suitable for use herein include Actiwhite®(Cognis), Emblica® (Rona), Azeloglicina (Sinerga) and extracts (e.g.mulberry extract).

The compositions may comprise an antimicrobial or antifungal active.Such actives are capable of destroying microbes, preventing thedevelopment of microbes or preventing the pathogenic action of microbes.A safe and effective amount of an antimicrobial or antifungal active maybe added to the present compositions, preferably, from about 0.001% toabout 10%, more preferably from about 0.01% to about 5%, and even morepreferably from about 0.05% to about 2% by weight of the composition.

Preferred examples of actives include those selected from the groupconsisting of salicylic acid, benzoyl peroxide, 3-hydroxy benzoic acid,glycolic acid, lactic acid, 4-hydroxy benzoic acid, acetyl salicylicacid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoicacid, cis-retinoic acid, trans-retinoic acid, retinol, phytic acid,N-acetyl-L-cystein, lipoic acid, azelaic acid, arachidonic acid,benzoylperoxide, tetracycline, ibuprofen, naproxen, hydrocortisone,acetominophen, resorcinol, phenoxyethanol, phenoxypropanol,phenoxyisopropanol, 2,4,4′-trichloro-2′-hydroxy diphenyl ether,3,4,4′-trichlorocarbanilide, octopirox, ciclopirox, lidocainehydrochloride, clotrimazole, climbazole, miconazole, ketoconazole,neocycin sulfate, and mixtures thereof.

The compositions may comprise a conditioning agent selected from thegroup consisting of humectants, moisturizers, or skin conditioners. Avariety of these materials can be employed and each can be present at alevel of from about 0.01% to about 40%, more preferably from about 0.1%to about 30%, and even more preferably from about 0.5% to about 15% byweight of the composition. These materials include, but are not limitedto, guanidine; urea; glycolic acid and glycolate salts (e.g. ammoniumand quaternary alkyl ammonium); lactic acid and lactate salts (e.g.ammonium and quaternary alkyl ammonium); aloe vera in any of its varietyof forms (e.g., aloe vera gel); polyhydroxy compounds such as sorbitol,mannitol, glycerol, hexanetriol, butanetriol, propylene glycol, butyleneglycol and hexylene glycol; polyethylene glycols; sugars and starchderivatives (e.g. alkoxylated glucose, fructose, sucrose, trehalose);hyaluronic acid; lactamide monoethanolamine; acetamide monoethanolamine;sucrose polyester; petrolatum; and mixtures thereof.

The compositions can comprise one or more thickening agents, preferablyfrom about 0.05% to about 10%, more preferably from about 0.1% to about5%, and even more preferably from about 0.25% to about 4%, by weight forthe composition. Nonlimiting classes of thickening agents include thoseselected from the group consisting of:

a. Carboxylic Acid Polymers

These polymers are crosslinked compounds containing one or more monomersderived from acrylic acid, substituted acrylic acids, and salts andesters of these acrylic acids and the substituted acrylic acids, whereinthe crosslinking agent contains two or more carbon-carbon double bondsand is derived from a polyhydric alcohol.

Examples of commercially available carboxylic acid polymers usefulherein include the Carbomers, which are homopolymers of acrylic acidcrosslinked with allyl ethers of sucrose or pentaerytritol. TheCarbomers are available as the Carbopol® 900 series from NoveonCorporation (e.g. Carbopol® 954). In addition, other suitable carboxylicacid polymeric agents include copolymers of C₁₀₋₃₀ alkyl acrylates withone or more monomers of acrylic acid, methacrylic acid, or one of theirshort chain (i.e. C₁₋₄ alcohol) esters, wherein the crosslinking agentis an allyl ether of sucrose or pentaerytriotol. These copolymers areknown as Acrylates/C₁₀₋₃₀ Alkyl Acrylate Crosspolymers and arecommercially available as Carbopol® 1342, Carbopol® 1382, Ultrez® 21,Pemulen® TR-1, and Pemulen® TR-2, from Noveon Corporation.

b. Taurate Polymers

The compositions of the present invention can optionally comprisecrosslinked taurate polymers useful as thickeners or gelling agentsincluding anionic, cationic and nonionic polymers. Examples includeHydroxyethyl Acrylate/Sodium Acryloyidimethyl Taurate (e.g. Simulgel® NSand INS100), Acrylate/Sodium Acryloyidimethyl Taurate (e.g. Simulgel®EG), Sodium Acryloyldimethyl Taurate (e.g. Simulgel® 800) and AmmoniumAcryloyidimethyl Taurate/Vinyl Pyrrolidone (e.g. Aristoflex® AVC).

c. Polyacrylamide Polymers

The compositions of the present invention can optionally comprise vinylpolymerized polyacrylamide polymers, especially nonionic polyacrylamidepolymers including substituted branched or unbranched polymers.Preferred among these polyacrylamide polymers is the nonionic polymergiven the CTFA designation polyacrylamide and isoparaffin and laureth-7,available under the tradename Sepigel® 305 from Seppic Corporation.

Other polyacrylamide polymers useful herein include multi-blockcopolymers of acrylamides and substituted acrylamides with acrylic acidsand substituted acrylic acids. Commercially available examples of thesemulti-block copolymers include Hypan SR150H, SS500V, SS500W, SSSA100H,from Lipo Chemicals, Inc.

d. Polysaccharides

A wide variety of polysaccharides are useful herein. “Polysaccharides”refer to gelling agents that contain a backbone of repeating sugar(i.e., carbohydrate) units. Nonlimiting examples of polysaccharidegelling agents include those selected from the group consisting ofcellulose, carboxymethyl hydroxyethylcellulose, hydroxyethylcellulose,hydroxyethyl ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methyl hydroxyethylcellulose, microcrystallinecellulose, sodium cellulose sulfate, and mixtures thereof.

e. Gums and Clays

Other thickening and gelling agents useful herein include materials thatare primarily derived from natural sources. Nonlimiting examples includematerials selected from the group consisting of acacia, agar, algin,alginic acid, ammonium alginate, amylopectin, calcium alginate, calciumcarrageenan, carnitine, carrageenan, dextrin, gelatin, gellan gum, guargum, guar hydroxypropyltrimonium chloride, hectorite, laponite,bentonite, hyaluronic acid, hydrated silica, hydroxypropyl chitosan,hydroxypropyl guar, karaya gum, kelp, locust bean gum, natto gum,potassium carrageenan, propylene glycol alginate, sclerotium gum, sodiumcarboxymethyl dextran, sodium carrageenan, tragacanth gum, xanthan gum,and mixtures thereof.

The compositions of the present invention may contain one or moreparticulate materials. Nonlimiting examples of particulate materialsinclude colored and uncolored pigments, interference pigments, inorganicpowders, organic powders, composite powders, optical brightenerparticles, and combinations thereof. Particulate materials may bepresent from about 0.01% to about 20%, more preferably from about 0.05%to about 10%, still more preferably from about 0.1% to about 5%, byweight of the composition.

Particulate materials useful herein include but are not limited tobismuth oxychloride, sericite, mica, mica treated with barium sulfate ortitanium dioxide, zeolite, kaolin, silica, boron nitride, lauroyllysine, nylon, talc, styrene, polystyrene, ethylene/acrylic acidcopolymer, aluminum oxide, silicone resin, barium sulfate, calciumcarbonate, cellulose acetate, PTFE, polymethyl methacrylate, starch,modified starches, silk, glass, and mixtures thereof. Preferred organicpowders/fillers include polymeric particles chosen from themethylsilsesquioxane resin microspheres such as those sold by ToshibaSilicone under the name Tospearl 145A; microspheres ofpolymethylmethacrylates such as those sold by Seppic under the nameMicropearl M 100; the spherical particles of crosslinkedpolydimethylsiloxanes, especially such as those sold by Dow CorningToray Silicone under the name Trefil E 506C or Trefil E 505C; sphericalparticles of polyamide and more specifically Nylon 12, especially suchas those sold by Atochem under the name Orgasol 2002N Nat C05;polystyrene microspheres such as those sold by Dyno Particles under thename Dynospheres; ethylene acrylate copolymer sold by Kobo under thename FloBead EA209; PTFE; polypropylene; aluminum starchoctenylsuccinate such as sold by National Starch under the name Dry Flo;microspheres of polyethylene such as those sold by Equistar under thename of Microthene FN510-00; silicone resin; platelet shaped powder madefrom L-lauroyl lysine, and mixtures thereof. Especially preferred arespherical powders with an average primary particle size from 0.1 to 75microns, preferably from 0.2 to 30 microns.

The topical compositions of the subject invention include but are notlimited to lotions, milks, mousses, serums, sprays, aerosols, foams,sticks, pencils, gels, creams and ointments. The compositions may alsobe applied via a woven or nonwoven synthetic and/or natural fiberedtextile (wipe or towelette).

Except in the operating and comparative examples, or where otherwiseexplicitly indicated, all numbers in this description indicating amountsof material ought to be understood as modified by the word “about”.

The term “comprising” is meant not to be limiting to any subsequentlystated elements but rather to encompass non-specified elements of majoror minor functional importance. In other words the listed steps,elements or options need not be exhaustive. Whenever the words“including” or “having” are used, these terms are meant to be equivalentto “comprising” as defined above.

All documents referred to herein, including all patents, patentapplications, and printed publications, are hereby incorporated byreference in their entirety in this disclosure.

The following examples will more fully illustrate the embodiments ofthis invention. All parts, percentages and proportions referred toherein and in the appended claims are by weight unless otherwiseillustrated.

EXAMPLES 1-4

The following are non-limiting examples of sunscreen compositionsaccording to the present invention.

Example 1 2 3 4 Phase A DC-9040 ™ 8.60 3.00 37.00 5.00 Sylvaclear ™ PA1200V 4.00 6.50 — — and OMC Composite Sylvaclear ™ AF 1900V — — 4.006.50 and OMC Composite Benzophenone-3 3.00 3.00 3.00 3.00Polymethylsilsequioxane 4.00 4.00 4.00 4.00 Cyclomethicone 11.43 0.508.22 11.33 Dimethicone PEG-10/15 5.37 5.25 2.75 5.40 CrosspolymerPolyethylene wax 3.54 — 2.41 2.05 Fragrance 0.10 0.10 0.10 0.10 TitaniumDioxide (Coated — — — 0.65 With 5% Dimethicone) Titanium Dioxide (Coated5.00 0.01 1.00 — Mica Coated with 6% Methicone) Phase B Glycerin 10.0010.00 10.00 10.00 Dexpanthenol 0.50 0.50 0.50 0.50 Pentylene Glycol 3.003.00 3.00 3.00 Hexamidine Disethionate 0.10 0.10 0.10 0.10 Niacinamide5.00 5.00 5.00 5.00 Methylparaben 0.20 0.20 0.20 0.20 Ethylparaben 0.050.05 0.05 0.05 Sodium citrate 0.20 0.20 0.20 0.20 Citric Acid 0.03 0.030.03 0.03 Sodium Benzoate 0.05 0.05 0.05 0.05 Sodium Chloride 0.50 0.500.50 0.50 FD&C Red #40 (1%) 0.05 0.05 0.05 0.05 Water Qs Qs Qs Qs

The formulas in the examples are prepared in a suitable container firstby combining the ingredients of Phase A. In a separate suitablecontainer, combine the ingredients of Phase B. Heat each phase to 73C-78° C. while mixing each phase using a suitable mixer (e.g. Anchorblade, propeller blade, IKA T25) until each reaches temperature and ishomogenous. Slowly add Phase B to Phase A while continuing to mix PhaseA. Continue mixing until batch is uniform. Pour product into suitablecontainers at 73-78° C. and store at room temperature. Alternatively,continuing to stir the mixture as temperature decreases results in lowerobserved hardness values at 21° C. and 33° C.

EXAMPLE 5

A series of comparative experiments were conducted to demonstrateaspects of the present invention. These experiments are based upontesting of the formulas outlined under Table I.

TABLE I Formula (Weight %) Component 1 2 3 4 5 6 7 8 DC 9045 Silicone26.00  26.00  26.00  26.00  26.00  26.00  26.00  26.00  Elastomer BlendCetyl Alcohol 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Parsol MCX 6.002.00 0.00 0.00 0.00 0.00 0.00 0.00 (octylmethoxycinnamate)Caprylic/Capric 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Triglyceride DC200 (Dimethicone) — 2.00 4.00 4.00 4.00 4.00 4.00 2.00 DC 245 — 2.002.00 2.00 2.00 2.00 2.00 2.00 (Cyclopentasiloxane) Silsoft 034 (Caprylyl2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Methicone) Disteardimonium 0.400.40 0.40 0.40 0.40 0.40 0.40 0.40 Hectorite PEG-10 Dimethicone 2.602.60 2.60 2.60 2.60 2.60 2.60 2.60 Titanium Dioxide 0.50 0.50 0.50 0.500.50 0.50 0.50 0.50 Timiron MP-111 (Mica 0.50 0.50 0.50 0.50 0.50 0.500.50 0.50 Coated With Titanium Dioxide) Glydant Plus Liquid 0.20 0.200.20 0.20 0.20 0.20 0.20 0.20 Disodium EDTA 0.05 0.05 0.05 0.05 0.050.05 0.05 0.05 UV Pearls ™ — — — 5.50 — — — — Suncap 665 ™ — — — — 9.50— — — Sylvaclear/PA 1200V ™ — — — — — 4.00 — — Composite (1:1 OMC)Sylvaclear PA1200V ™ — — — — — — 4.00 4.00 neat (no sunscreen) AcetamideMEA 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Glycerin 5.00 5.00 5.00 5.005.00 5.00 5.00 5.00 Glycol Acid (70%) 5.71 5.71 5.71 5.71 5.71 5.71 5.715.71 Potassium hydroxide 6.24 6.24 6.24 6.24 6.24 6.24 6.24 6.24 Dequest2006 0.49 0.49 0.49 0.49 0.49 0.49 0.49 0.49 Conjugated Linoleic Acid1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Butylhydroxytoluene 0.20 0.200.20 0.20 0.20 0.20 0.20 0.20 Water, Deionized Balance Balance BalanceBalance Balance Balance Balance balance

Optical Measurements

Opacity is the measure of intensity attenuation of a transmitted lightbeam shone perpendicular to a medium or film. The higher the direct beamattenuation, the greater will be the opacity. The source of the lightbeam attenuation is two fold: A) Some of the original light is reflectedback from the film/medium. This gives the film/medium a truewhite/opaque appearance with great hiding power. Using pigment-gradeTiO₂ in a formulation will give the effect. B) Some of the light isdeflected from the straight beam path but still transmitted through thefilm/medium. In effect, the film/medium goes from being transparent totranslucent, creating a “blurred” image. Another term for this is softfocus.

Procedure: Apply (or draw down) a 3 mil (76.2 μm) film of a formulationusing a draw down bar on to a plastic overhead transparency sheet. Letthe film dry for 2 hours at room temperature.

Take the coated overhead transparency and place it in an InstrumentSystems goniospectrophotometer. Set the light source and detectorarrayed in a straight line perpendicular to the coated transparency. Thelight source (set at 209 million Watt-nm/cm², which serves as areference for all Transmission Intensity Values reported herein) isturned on and the measurement of the transmitted light intensity ismade. Further measurements are made by moving the detector 10, 30, 40,50 degrees away from the direct transmission normal. These valuesindicate the extent of soft focus light scattering. The Reflectance or“radiance” of a product is determined in the same way as opacity/softfocus light scattering, except for the positions of the light source anddetector. The detector is 30 degrees on one side of thenormal/perpendicular, while the light source is 20 degrees on the otherside. To determine the extent of the intensity attenuation, compare theintensity value to that of an uncoated overhead transparency. Thedifference between these two values is the extent of the attenuation oropacity.

SPF Measurements

Sun protection factor (SPF) was measured in vitro using an OptometricsSPF 290 instrument. The test procedure required calibration of themonochrometer and sample stage of the Optometrics SPF 290 instrument.Thereafter the instrument was calibrated with a blank sample quartzplate (10 cm×10 cm and 3 mm thickness). Calibration zeros the UVdetector. Formula is applied to a plate using an 1 mil draw-downapplicator. This leaves a film of 2 mg/cm². The film is about to dry for30 minutes. Subsequently an SPF reading is taken on the dried film usingthree measurements on different parts of the coated quartz plate andrecording an average value.

Soft focus results with the formulations are reported in Table II.

TABLE II Transmission Intensity Values* Intensity Formula Admisibility 12 3 4 5 6 7 8 Range Variable 6% 2% 0% OMC UV Pearls ™ SunCaps ™Sylvaclear ™ Sylvaclear ™ Sylvaclear ™ Component External External 664Composite (with (without OMC) (without OMC) OMC OMC OMC) and 2% ExternalOMC Transmission Angle in Degrees  0 7.1 M 6.5 M 6.0 M 6.2 M 6.4 M 4.6 M5.3 M 6.2 M 4.0 to 7.0 million 10 1.0 M 1.0 M 1.5 M 1.4 M 1.4 M 18. M1.6 M 1.3 M 1.0 to 2.0 million 30 115K 122K 131K 123K 122K 139K 134K128K 120 to 140 thousand 40  56K  63K  70K  62K  63K  79K  73K  68K 60to 80 thousand 50  37K  42K  51K  44K  43K  60K  54K  48K 40 to 60thousand Reflection Angle in Degrees 30 138K 143K 151K 153K 150K 164K155K 146K 140 to 170 thousand SPF Value 15 8 4 15 15 20 4 8 *Values arethe Intensity of light scatter (units are W-nm/cm2)

All the composites (UV Pearls™, SunCaps™, Sylvaclear/Sunscreen) wereformulated to deliver 2% octylmethoxycinnamate (OMC) to the overallcosmetic composition. UV Pearls™ is sold by the Rona Division of EMDChemicals. Their preparation is described in U.S. Pat. No. 7,264,795herein incorporated by reference. UV Pearls™ are sold as particulatesdispersed in an aqueous carrier; the particulates areoctylmethoxycinnamate coated with silica, polyvinylpyrrolidone and minorfunctional ingredients. SunCaps™ are sold by Particle Sciences, Inc. ofBethlehem, Pa. and described in U.S. Pat. No. 5,733,531 hereinincorporated by reference. These particles include octylmethoxycinnamateencapsulated in an binder that includes beeswax, carnauba wax, VinylPyrrolidone/Eicosene Copolymer and emulsifiers. The encapsulates aresupplied as an aqueous dispersion containing up to 65% solids.

The Sylvaclear polymer sunscreen composite in Formula 6 (presentinvention) maintains the soft focus benefits of the 0% OMC Formulas andeven improves on the high angle soft focus profile. A further benefit ofFormula 6 is that it still exhibits an SPF higher than 15. Opacity isimproved (lowered) and Reflectance increased. All of this shifts thetransmission soft focus curves and reflection to maximum performancewithin the Intensity Admissibility range. By contrast, Formulas 4 and 5containing UV Pearls™ and SunCaps™ have a negative impact on soft focus.Values are lower than the 0% OMC Formula 3. Addition of the Sylvaclearresin alone along with external 2% OMC (not within a binder) as inFormula 8 yields a slight improvement to the high angle soft focus andReflectance relative to that of Formula 2. However, the SPF of 8 isidentical for both Formula 2 and 8. Contrast this to the much bettersoft focus, Reflectance and sunscreen activity (SPF of 20) of Formula 6that blends 2% OMC within the polymer composite.

1. A cosmetic water-in-oil emulsion composition comprising: (i) from about 0.1 to about 20% by weight of composite particles comprising organic sunscreen agent and a condensation polymerized polyamide mixed together to form each of the composite particles in a relative weight ratio of about 5:1 to about 1:10; (ii) from about 0.1 to about 30% by weight of an emulsifying silicone surfactant sufficient to form the water-in-oil emulsion; (iii) from about 1 to about 90% by weight of the composition of an oil phase; and (iv) from about 5 to about 90% by weight of the composition of water.
 2. (canceled)
 3. The composition according to claim 1 wherein the composite particles have an average particle size ranging from about 10 to about 2,000 nm.
 4. The composition according to claim 1 wherein the composite particles have an average particle size ranging from about 100 to about 1,500 nm.
 5. The composition according to claim 1 wherein the polyamide is a polyalkyleneoxypolyamide resin.
 6. The composition according to claim 1 wherein the polyamide is an ester-terminated poly(ester-amide) resin.
 7. The composition according to claim 1 wherein the sunscreen agent is octylmethoxycinnamate, Benzophenone-3 and mixtures thereof. 